Anhydride polymers for use as curing agents in epoxy resin-based underfill material

ABSTRACT

An underfill material is presented that may be used between an electrical component and a substrate. The underfill material may be a cured epoxy resin composition comprising a liquid or semisolid epoxy resin and a polyfunctional anhydride polymer and/or oligomer curing agent. The use of anhydride polymers and/or oligomers decrease the volatilization of the composition, thereby reducing the porosity of the underfill material. By changing substituents of the anhydride polymer and/or oligomer, the underfill material may be designed to modify viscosity, decrease moisture adsorption, volatilization and modulus, improve mechanical properties, and enhance adhesion.

RELATED APPLICATIONS

The application is a continuation of U.S. patent application Ser. No.10/616,085, filed on Jul. 8, 2003, which issued on May 9, 2006, as U.S.Pat. No. 7,041,736, which is a divisional application of U.S. patentapplication Ser. No. 10/028,393, filed on Dec. 21, 2001, which issued onSep. 16, 2003, as U.S. Pat. No. 6,620,512.

FIELD OF THE INVENTION

The present invention relates to a connection between an electricalcomponent and a substrate. More particularly, the present inventionrelates to controlling the coefficient of thermal expansion for anunderfill between a chip and a substrate (e.g., in flip chip mounting).

BACKGROUND OF THE INVENTION

Microelectronic devices contain millions of electric circuit components,including transistors assembled in integrated circuit chips, resistors,and capacitors. These electronic components are interconnected to formthe circuits, and are eventually connected to and supported on asubstrate. The connections are made between electrical terminations onthe electronic component and corresponding electrical terminations onthe substrate. One method for making these connections includes aflip-chip mounting technique. Flip chips are made by positioning thesilicon die (“the chip”) with the active side (“the face”) down on thesubstrate. Bond pads on the face of the chip are connected by solderbumps or other interconnects to the substrate. During reflow, the solderbumps complete the electrical connections from the active circuitry ofthe die to the substrate.

During subsequent manufacturing steps, an electronic assembly issubjected to cycles of elevated and lowered temperatures. Because thereis a significant difference in the coefficient of thermal expansion(CTE) for the chip, the interconnect material, and the substrate, thisthermal cycling can stress the components of the assembly and causefailure at the interconnect points, thereby destroying the functionalityof the circuit. To help prevent such failure, the space between the chipand the substrate is underfilled with a dielectric organic material.Once cured, the underfill acts as a buffer between the chip and thesubstrate and functions to distribute the CTE-induced stress over theentire surface, thereby greatly increasing the life of the finishedpackage. Underfill material also protects the interconnects frommoisture and other forms of contamination, and thus, overmolding theback of the chip with epoxy is unnecessary.

The CTE of the underfill material is critical to the reliability of thedevice because the underfill material compensates for the difference inCTE between the substrate and the chip. In order to reduce solder jointfatigue and extend solder joint life, the CTE of the underfill materialshould be in the range of about 20 to 40 ppm/° C. at temperatures belowits glass transition temperature (T_(g)).

Underfilling may occur after the reflow of the metallic or polymericinterconnect, or it may occur simultaneously with the reflow. Ifunderfilling occurs after reflow of the interconnect, a predeterminedamount of the underfill material may be dispensed at one or more sidesof the gap between the chip and the substrate. The material will flow bycapillary action into the gap, thereby contacting the solder bumps. Someof the defects that can originate during the flow of fluid underfillinclude delaminations, where the underfill fails to wet and adhere to asurface, and voids, where contamination causes local variations in thespeed of flow and causes bubbles to be trapped. Reducing the viscosityof underfill material, however, enables the material to flow more easilyinto the small gaps between the silicon die and the substrate. Theunderfill material is subsequently cured to reach its optimized finalproperties.

If underfilling occurs simultaneously with reflow of the solder orpolymeric interconnects, the underfill material first is applied toeither the substrate or the chip. Then terminals on the chip andsubstrate are aligned and contacted and the assembly is heated to reflowthe metallic or polymeric interconnect material. During this heatingprocess, curing of the underfill material occurs simultaneously withreflow of the metallic or polymeric interconnect material.

DETAILED DESCRIPTION

In general an underfill material, when cured, is a composite materialmade up of cross-linked resin. Generally, cross-linking is theattachment of two polymer chains by bridges of an element, a moleculargroup, or a compound, and in general will occur upon heating. Polymerscan be prepared at a variety of cross-link density—from tacky,elastomeric to tough, glassy—by the judicious choice and amount of mono-or polyfunctional compounds, resins, and crosslinking agents. Thegreater proportion of polyfunctional compounds reacted, the greater thecross-link density. If thermoplastic properties are desired, underfillmaterial may be prepared from different compounds to limit thecross-link density. The cross-link density may also be controlled togive a wide range of T_(g) in the cured underfill in order to withstandsubsequent processing and operation temperatures.

Presently, the anhydrides that are used in underfill material are smallmolecules that have a tendency to volatize during the curing process.Such volatilization leads to porosity during underfill cure, which leadsto system failure (e.g., delamination, voids, and moisture penetration).Further, the presently-used anhydrides typically only perform onefunction, i.e. cross-linking.

An embodiment of the present invention relates to a curable liquid orsemisolid underfill material composition comprising resin such as epoxyresin and silica particles and curing agents such as polyfunctionalanhydride polymers and oligomers. The use of low molecular weightanhydride polymers and/or oligomers facilitates the cure process bydecreasing the volatilization of the composition, and thereby reducingporosity in the cured underfill materials. Further, using anhydrideoligomers and/or polymers in the underfill material creates a uniqueopportunity to design various oligomers and/or polymers that may reactwith the epoxy matrix, thereby crosslinking the matrix, and may alsoprovide a structure that may be designed, by substituting different Rgroups, to modify viscosity, decrease moisture absorption,volatilization and modulus, improve mechanical properties, and/orenhance adhesion. The underfill material may also optionally includecatalysts for promoting cross-linking and to control cure time,elastomers for toughening, and/or coupling agents, fillers, fluxingagents, and other additives for flow modification and adhesion. Theunderfill material may also have a higher T_(g), thereby resulting inrobust material for 260° C. reflow conditions.

The underfill material includes resin, which may be present in an amountof from about 25 to about 100 weight percent based on the organiccomponents present. Suitable resins include epoxy resin such ascycloaliphatic epoxy resins, bisphenol-A type epoxy resins, bisphenol-Ftype epoxy resins, novolac epoxy resins, biphenyl type epoxy resins,naphthalene type epoxy resins, dicyclopentadiene-phenol type epoxyresins, and mixtures thereof.

The curing agents comprise polyfunctional, low molecular weightanhydride polymers and/or oligomers. In accordance with an embodiment ofthis invention, the curing agents may include these polymers and/oroligomers in combination with other compounds. The polymers and/oroligomers may be present in the curable underfill material compositionin an amount of from about 5 to about 25 weight percent based on totalweight of the resin and catalysts. Preferred curing agents includeolefin/maleic anhydride copolymers, such as, styrene/maleic anhydride,cyclohexane/maleic anhydride, norbornene/maleic anhydride copolymers. Byway of example, the following chemical schematic shows a low-cost, lowmolecular weight polymeric cross-linker that may be used in an underfillcomposition:

where n is 0 to 3, n′ is 5 to 50, and R is selected from the groupconsisting of alkyl, aryl, substituted aryls, esters, ethers, lactones,anhydrides, alcohols, nitriles, epoxy, and mixtures thereof.

The underfill material composition may include a catalyst, therebyeffecting the desired behavior of the formulation. For instance, inaddition to controlling the rate of the reaction, catalysts may be usedto promote cross-linking and/or to control the curing time of the resin.Suitable catalysts include imidazoles, phosphines, dicyanamide, andsubstituted dicyamide compounds.

The anhydride polymers and/or oligomers may contain different R groups,which may decrease moisture absorption, volatilization and modulus, mayimprove mechanical properties, and/or may enhance adhesion. The R groupmay be nitriles, acids, and/or alcohols. By way of example, thefollowing structural schematics show variations of polymeric anhydridecross-linkers.

Preferably, the underfill provides strength to the composite polymer andto the resin bonds with the chip and substrate. Also, the underfillmaterial may help to mechanically interlock the chip to the substrate,so it may be desirable for the underfill to exhibit good adhesion toboth the die and the substrate. In order to improve the adhesionproperty of the underfill, coupling agents are widely used. Examples ofsuitable coupling agents include silanes, titanates, zirconates,aluminates, silicate esters, metal acrylates or methacrylates, compoundscontaining a chelating ligand (e.g., phosphine, mercaptan,acetoacetate), and/or mixtures thereof. Certain coupling agents, such astitanate and zirconate, may also catalyze the curing reaction of theepoxy underfill, thereby lowering the onset temperatures of curing andincreasing the viscosity of the underfill material during storage at lowtemperatures. The kinds and amounts of coupling agents that may be usedare known to those skilled in the art.

The underfill composition may also include a filler material, which isused to adjust the CTE to more closely mirror that of the interconnect.Suitable fillers include silica, graphite, aluminum nitride, siliconnitride, silicon carbide, boron nitride, diamond dust, and clays.Typically, the fillers may be present in an amount of about 20 to about80 weight percent of the total underfill composition. Further, usingwell-known techniques, the fillers may be treated to make the fillerhydrophobic by silylating agents and/or agents reactive to the adhesivematrix, such as by using coupling agents.

The underfill material may also contain compounds that increaseflexibility and toughness in the resultant cured composition. Suchcompounds may be any thermoset or thermoplastic material having a T_(g)of 50° C. or less. Suitable compounds include polyacrylates, polymerizedTHF (tetrahydrofuran), carboxy-terminated butyronitrile rubber, andpolypropylene glycol. When present, these compounds may be in an amountof from about 10 to about 20 weight percent of the epoxy resin.

Siloxanes may also be added to the underfill material compositions toprovide elastomeric properties. Suitable elastomers includemethacryloxypropyl-terminated polydimethyl siloxanes, andaminopropyl-terminated polydimethylsiloxanes. Other additives, such asfluxing agents, may also be added as needed. The kinds and amounts ofelastomers and fluxing agents that may be used are known to thoseskilled in the art.

In general, the underfill material may be cured within a temperaturerange of from about 130° C. to about 170° C. and within about 5 minutesto about 4 hours. The time and temperature curing profile for eachunderfill material, however, may vary.

The underfill material may be prepared, for example, by simultaneouslyor separately agitating, dissolving, mixing and dispersing the epoxyresin, and curing agent, and optionally catalysts, elastomers, couplingagents, fillers, fluxing agents and/or flow and adhesion agents. Thedevice for mixing, agitating, and dispersing is not critical although,an attritor, three-roll mill, ball mill or planetary mixer each equippedwith agitating and heating means may generally be used. A suitablecombination of these devices may also be useful.

The curable underfill material composition containing low molecularweight anhydride polymers and/or oligomers may be applied using astandard capillary flow process or assisted flow process. The underfillmaterial may be used for new lead free under bump metallurgy (i.e.,SnAgCu, SnAg, SnCu) and may be applied with other newer processes suchas no-flow underfills, which, if properly formulated, may significantlydecrease manufacturing cost by eliminating the fluxing process, theunderfill flow process, and the underfill cure process. According to anembodiment of the present invention, such material may be used withlead-free solder materials or with an instant chip joining process.

EXAMPLES

Examples of the invention are given below by way of illustration and notby way of limitation.

Example 1

Styrene/maleic anhydride copolymer (2 wt %) of a molecular weight ofabout 1600 g/mole and the catalyst imidazole (1 wt %) were added tobisphenol F epoxy resin (4 grams). Scheme 6 shows the structure of thecomposition. The resin was heated to about 70° C. and mixed thoroughlyuntil all of the polymer was observed to dissolve in the epoxy resin,thereby forming a homogeneous solution. The solution was cooled to roomtemperature and cured at about 165° C. for about 2 hours. A cross-linkedhard transparent polymer was obtained.

Example 2

Styrene/maleic anhydride copolymer (5 wt %) of a molecular weight ofabout 1600 g/mole and the catalyst imidazole (1 wt %) were added tobisphenol F epoxy resin (4 grams). Using the same process as describedin Example 1, a cross-linked hard transparent polymer was obtained.

Example 3

Styrene/maleic anhydride copolymer (7.5 wt %) of a molecular weight ofabout 1600 g/mole and the catalyst imidazole (1 wt %) were added tobisphenol F epoxy resin (4 grams). Using the same process as describedin Example 1, a cross-linked hard transparent polymer was obtained.

Example 4

Styrene/maleic anhydride copolymer (10 wt %) of a molecular weight ofabout 1600 g/mole and the catalyst imidazole (1 wt %) were added tobisphenol F epoxy resin (4 grams). Using the same process as describedin Example 1, a cross-linked hard transparent polymer was obtained. ByDMA (Dynamic Mechanical Analysis), the T_(g) of the polymer was found tobe 55° C. Using TMA (Thermal Mechanical Analysis) measurements, thecoefficient of thermal expansion of the polymeric system was found to be63 ppm/° C.

Example 5

Styrene/maleic anhydride copolymer (25 wt %) of a molecular weight ofabout 1600 g/mole and the catalyst imidazole (1 wt %) were added tobisphenol F epoxy resin (4 grams). Using the same process as describedin Example 1, a cross-linked hard transparent polymer was obtained. ByDMA, the T_(g) of the polymer was found to be 75° C. Using TMAmeasurements, the coefficient of thermal expansion of the polymericsystem was found to be 57 ppm/° C.

Example 6

To determine the percent weight during cure, the following experimentwas conducted.

Styrene/maleic anhydride copolymer (10 wt %) of a molecular weight ofabout 1600 g/mole and the catalyst imidazole (1 wt %) were added tobisphenol F epoxy resin (4.0 grams). The resin was mixed thoroughly toform a homogeneous solution. A small amount of the resin was heated fromabout 25° C. to about 165° C. and held for 2 hours usingthermogravimetric analysis. Weight loss during cure was measured to be 1wt %.

A similar experiment was conducted with a monomeric anhydride sample.Cyclohexyl anhydride copolymer (1.18 grams) and the catalyst imidazole(1 wt %) were added to bisphenol F epoxy resin (2.0 grams). Weight lossduring cure was measured to be 3.6 wt %.

Example 7

Cyclic olefin (10 wt %) containing various functional groups (e.g.,epoxies, esters, ethers, alcohols, anhydrides, nitriles)/maleiccopolymer of a molecular weight <5000 g/mole and the catalyst imidazole(1% wt) are added to epoxy resin (4 grams) such as bis F, napthelene,and the like. The resin is heated to about 70° C. and mixed thoroughlyuntil all of the polymer is observed to form a homogeneous solution. Thesolution is cooled to room temperature and cured at about 165° C. forabout 2 hours. A cross-linked hard hazy polymer is obtained.

Example 8 Use of Polymeric Anhydride Formulation as Underfill Material

The product in example 4 was evaluated as an underfill on a flip chippackage. The product was dispensed on one side of a die of a flip chippackage that had been pre-baked. The substrate was held at about 70° C.for about 1 minute for the underfill to flow through the gap between thedie and the substrate. After 1 minute, the package was removed and wetCSAM (C-mode Scanning Acoustic Microscopy) was conducted to confirm fullcoverage of the underfill and also to confirm absence of any voids. Theunit was later cured at about 165° C. for about 2 hours, thereby curingthe underfill material. The fillet (underfill around the die) wasconfirmed to be completely cured. CSAM of the package post cure was alsoobserved to be clean with no voiding or delamination as shown below.

Although embodiments are specifically illustrated and described herein,it is to be appreciated that modifications and variations of the presentinvention are covered by the above teachings and are within the purviewof the appended claims, without departing from the spirit and intendedscope of the invention.

1. An underfill composition comprising: an epoxy resin; and a curingagent selected from the group consisting of low molecular weight maleicanhydride polymers comprising cyclohexane or bridged cyclohexane havingthe following structural formula,

where n is 0, 2 or 3, n′ is 5 to 50, and R is selected from the groupconsisting of alkyl, aryl, substituted aryls, esters, ethers, lactones,anhydrides, alcohols, nitriles, epoxy, carboxylic acids and mixturesthereof, maleic anhydride polymers comprising norbornene having thefollowing structural formula:

where n is 1, n′ is 5 to 50, and R is selected from the group consistingof ethers, lactones, anhydrides, alcohols, nitriles, epoxy, carboxylicacids, and styrene/maleic anhydride polymers having a molecular weightof about 1600 g/mole, and mixtures thereof.
 2. The composition accordingto claim 1 further comprising at least one component selected from thegroup consisting of catalyst, elastomer, coupling agent, filler, fluxingagent, flow agent, adhesion agent, and mixtures thereof.
 3. Thecomposition according to claim 2 wherein the catalyst is selected fromthe group consisting of imidazoles, phosphines, dicyanamide, andsubstituted dicyamide compounds.
 4. The composition according to claim 2wherein the curing agent is in an amount of from about 5 to about 25weight percent based on total weight of the resin and the catalyst. 5.An underfill material that is a cured epoxy resin compositioncomprising: one of a liquid and semisolid epoxy resin; and a curingagent selected from the group consisting of low molecular weight maleicanhydride polymers comprising cyclohexane or bridged cyclohexane havingthe following structural formula,

where n is 0, 2 or 3, n′ is 5 to 50, and R is selected from the groupconsisting of alkyl, aryl, substituted aryls, esters, ethers, lactones,anhydrides, alcohols, nitriles, epoxy, carboxylic acids and mixturesthereof, maleic anhydride polymers comprising norbornene having thefollowing structural formula:

where n is 1, n′ is 5 to 50, and R is selected from the group consistingof ethers, lactones, anhydrides, alcohols, nitriles, epoxy, carboxylicacids, and styrene/maleic anhydride polymers having a molecular weightof about 1600 g/mole, and mixtures thereof.
 6. The composition accordingto claim 5 further comprising at least one component selected from thegroup consisting of catalyst, elastomer, coupling agent, filler, fluxingagent, flow agent, adhesion agent, and mixtures thereof.
 7. Thecomposition according to claim 6 wherein the catalyst is selected fromthe group consisting of imidazoles, phosphines, dicyanamide, andsubstituted dicyamide compounds.
 8. The composition according to claim 6wherein the curing agent is in an amount of from about 5 to about 25weight percent based on total weight of the resin and the catalyst.